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#1 (permalink) Old 03-25-2005, 11:43 AM
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I took the following from another site, its in two parts and I left the copyright request in as you will see. This is the best article I have found on the subject and will be more accurate than most of the advise you will get on BMW forums. I will do two posts as it is long. Read it, I think you might be in for a surprise or two:



Someone in the octane thread asked for a chemist's view on the subject, so here's mine. However, first a view necessities and background:
Credentials:
Ph.D. Organic chemist, 21 years as a practising chemist, 28 US patents (many on gasoline additves), work for a major oil company that is a leading (by volume) retailer of gasoline in the world. I've had engine tests (meaning an engine on a fixed engine stand run by a computer) and road tests (meaning cars driven by humans -- some on a course, some not) run on gasoline additives I've invented (while employed at the oil company). These additives have been tested in the US, England, and France under a variety of conditions. Many of my additives have also been tested in the BMW test (10,000 miles). I'm still employed by said oil company.


Copyright:
This entire note is copyrighted by the author. Participants in this mail group may store and make one copy for their own use. Participants may refer to, copy, send, and re-send to particpants of this mail group and post or re-post sections of this note as long as this copyright notice is attached. Except for these specific exceptions, this note may not be copied, quoted, or transmitted in any form for profit or non-profit, or used for any type of publication without written permission from the author.

Corvette:
Mine is a 1979 that is on its second trip through the odometer (and its second engine, and third interior). I've owned it approximately 12 years, love it, and may never get rid of it.

Octane:
I've seen many consummer magazines tell their readers that they are wasting money to buy a higher octane gasoline if their car doesn't knock. If octane were not related to any other feature of the gasoline, I would agree. However, how companies get higher octane gasoline does make it different than regular and mid-grade gasoline. So the question to me then is, do these differences make a difference? The short answer is what do I use, and I use regular in all my cars and my truck. I use premium in my Corvette. Why? Because as any Corvette enthusiast (to separate us from people who merely own one -- no flames, please) knows, a Corvette is not a car, it's an experience. If you want to know the long answer keep reading.

Base gasoline:
Crude oil differs depending on where it's from, and consequently, what comes out of it when it's refined also differs. There are books on the subject and I can't possibly do the subject justice here. As the oil differs, what is available for blending and cutting is different. In the end, however, the refiner has to make economic choices, based on what's available to him from the oil he is refining, on how to get the required octane to sell (as well as meet MANY other criteria that make gasoline, gasoline -- again I can't do justice to it here). What I generally (but not exclusively) see is that BASE (no additve added to it -- you can't buy this, it isn't offered for sale) premium gasoline leaves less deposits behind than other grades. There are certain types of molecules in regular and mid-grade BASE gasolines that simply do not exist in premium gasoline that cause much of this. Additives (see definition below) are added to the gasoline to help get rid of these deposits, and modern additives do a marvelous job of this. What you buy is additized gasoline.

Blending components vs additives:
MTBE (methyl tertiary butyl ether -- this is ether) and ethanol are blending components, not additives. However, you'll see them called additives in many places by many people. Blending components are part of base gasoline. The simplest differentiation between an additve and a blending component is that the former are added in ppm (parts-per-million) levels; whereas, the latter are added in percentage quantities.

Brand of gasoline:
Some of you probably know this, others may be shocked by it. Oil companies swap base gasoline all the time. Let's say I have a refinery in Houston and you have one in Dallas. It makes little sense for me to truck my Houston gasoline to Dallas and for you to truck your gasoline from Dallas to Houston when gasoline is a commodity product. So, I let you draw 100,000 gallons of base gasoline from my storage tank in Houston for your Houston gas stations, and you let me draw 100,000 gallons of base gasoline from your Dallas holding tanks for my Dallas gas stations. That way, we both save on shipping. Yup, Texaco gasoline may have come from a Shell refinery and vice-versa. At a gasoline terminal you may see trucks from up to six different companies all loading at the SAME terminal (that for example may be supplied exclusively by Shell). What comes next, however, is what makes Texaco Texaco and Shell Shell. Additive. Each company has its own additive and adds it to the base gasoline. So while the base gasoline may be the same, the additive is different, and hence the brand of gasoline you use is different because of the additive, not the base gasoline.

Which additive is better?:
Given the above discourse, it's obvious that we all want the gasoline with the best additive. Unfortunately, it's not that simple. Additves respond differently in different base gasolines (even of the same grade). Also, some additves work better with gasolines used in a carbureted car vs one that uses fuel injection. On a practical level, additives are going to be developed today for today's cars -- meaning fuel injected cars. For Corvette owners who have carbureted Vettes (like me), this is unfortunate. Carbureted engines leave a LOT more deposits behind than fuel injected cars. From a regulatory stand point, California was the first to call for all gasolines to pass the BMW test (port-fuel-injected engine) in all grades of gasoline. Like all regulations, this one had various massages put to it, but the net effect was that all oil companies went to work developing additives that are a LOT better today than 10 years ago AND they are used in all grades (not just premium -- hence the argument to use premium to get a better additive went out the window).

Insider's trick on gasoline additives:
No matter what you do or what you drive, this trick will help you keep down deposits inside your engine. You see, additives themselves will make deposits and/or create a deposit that is different from the one made by base gasoline alone. If you think about this for a moment, you'll come to realize that your engine will build some kind of deposit based upon what additive you are using. Yes, it will build at a slower rate, but it will build deposits. At some level this will taper off (but this is maximum deposits and what Corvette owner wants that!). So what do you do? Simple, switch to a different brand of gasoline (this will almost assure you of getting a different additive but not always. Some companies buy additives from other companies, so it could be the same. More on this later). What this will do, is the new additve will look at the deposit formed from the old additive as foreign and begin removing it. Now after 5000 miles, you'll be rid of this deposit but you'll have a new one from your most recent additive, so switch back and start the process all over again. As an analogy, this is like building an immune response to an anti-biotic, so your doctor gives you a new one. I know of absolutely no additive that will work as well as switching back and forth between additives. On a molecular level this makes perfect sense.

So what's a Vette owner to do?:
(1) Whether you buy regular, mid-grade, or premium, use one brand for about 5000 miles, then switch to another brand for 5000 miles. I use Shell, then Chevron, then Exxon, then back to Shell, etc. (this is not an endorsement). These companies have historically had there own additive research groups/companies, so they'll likely use their own additive and not something they bought from each other. It is completely posible, however, to use a sequence like Amoco, Shell, Texaco and still come out fine. (Again these are not endorsements). I use three companies and 5000 miles based on what I've observed working in the research area. 7,000 miles and two different brands will still do wonders. As an aside, it takes most vehicles 7-13,000 miles to build their maximum deposit levels.

(2) If your Vette is carbureted or TBI, buy premium. These fuel-delivery systems build deposits rapidly and to much much higher levels than PFI (port fuel injection) systems You need every edge you can get (if you're an enthusiast). If I had a PFI Vette I'd still buy premium, but must tell you the effect will not be like in the carbureted version.
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#2 (permalink) Old 03-25-2005, 11:44 AM
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Part two of the above post, interesting Uh!

I've received a number of questions and many kind words (Thanks!). I thought I'd handle some of the repeated questions here.
Can I change between two different gasoline brands on every fill and get the same effect as switching brands at 5000 miles?
It's obvious from the responses and questions I've gotten on this that there's a lot of Brand loyalty out there (and the oil companies love you for it) and folks can't bear to be without their favorite gasoline for 5000 miles. Consequently I'll try to answer this question and at the same time try to help people stick with their favorite gasoline most of the time.

(1) I use the 5000 mile method because it works and because it's easy to remember. Every time the odometer hits a number divisible by 5, I switch. In reality, most of the deposit removal is accomplished in the first 1000 miles of new gas (maybe 3-5 tankfuls depending on how low you go before re-filling and what kind of mileage you get). 50% reduction in deposits is not unheard of over this time frame. You may get 10-20% more in the next 1000 miles, then you start to rebuild (actualy add to the residual deposits that remain). SO, if you want, you can go 5000 miles on your favorite brand, 1000 miles on your second favorite, and then go back again. For me, this is a pain in the butt. I'd have to remember to change brands at 5,6,11,12,17,18,23,24,000, etc miles. I'd rather just look at my odometer and say, "Hey, 55,000 miles. Time to change." As the saying goes, different strokes for different folks. Both methods will work a lot better than never changing brands (And again, I ONLY do this with my Vette. All my other vehicles get regular from where ever I happen to stop (although I only use a major brand).

(2) If you switch between Brand X and Y between fills, you're really just creating a new additve combination. As we don't run our tanks completely dry between fillups, you'd always have a residual amount of both additives in your tank at all times. This would likely create a different deposit than either X or Y by itself. By analogy this would be like taking a bucket of yellow paint and throwing it against a wall. The wall is yellow and represents deposits from additive X. Let's say your bucket is 1/4 full (like your gas tank) with yellow paint. Now you fill the bucket with blue paint (additive Y) and mix. The bucket now contains green paint. You throw it at the wall and the wall is now green. Next, take your 1/4 full bucket of green paint and fill it with yellow paint (X). You're gonna still have green paint, perhaps a different shade of green, but it is definitely not yellow and it's definitely not blue. If you repeat all these steps over and over, the wall will be green. It will not be yellow (X) or blue (Y). So all that you have done is create a new color (deposit type). If you want to change the color on the wall (other than shades of green), you'll have to switch to a new color (red?) and toss it at the wall several times before you can't see any green or have any green bleeding through your red. Of course with real deposits, we're removing them and changing what's left, not just covering them up, but hopefully this paint color analogy helps explain this.

Is gasoline dyed?
Many, many years ago it was. I'm not aware of any gas being dyed now. (Anybody remember Purple Martin high octane from the 60s? It looked like grape Kool Aid and was quite a marketing gimmick)

What gives gasoline color?
Many different things. Some bad, like PNAs (polynuclear aromatics) mentioned by Tracy, some not so bad. A lot of companies add anti-oxidants to keep down gum formation and that also helps color. However, a lot of gas stations are re-filled daily, so storage time isn't a problem. Premium is generally less colored due to how it's made (little or no PNAs, etc). Regular and midgrade are made from many things and generally have some color. I'd be concerned with any gas that was bright yellow or premium that was anything other than white or faintly yellow.

What about fuel injector additives?
Give the money to charity where it'll do some good; your fuel injectors will never know the difference. Other than a narrow window in 86-87 where some fuel injectors fouled, the modern (meaning post 87) injectors are of a design that won't foul unless you put some really old rotten gas through them. We had one guy in our group whose job it was to test our gas and competitors brands for injector fouling. He couldn't do it with '88 and newer injectors (with any brand of gas!). I mean he couldn't even get these injectors to foul a little. The only way he could run fouling tests was to buy a specific type and brand of pre-88 injectors (and he had a really hard time finding them. He bought up all he could find. -- Sorry can't tell you type and brand, but I doubt any of you have them). If you store your Vette over the winter and start it on gas that's been in the tank all those months, you will likely foul your injectors some. But if you can get it started and put fresh gas in it, all the additive packages (in the gas you buy) I've seen to date will clean the injectors in 1-2 tanks.

What about valve cleaner additives?
Can't recommend any specific brands, but there's one I know of that you add to your gas tank and it works pretty well. There is a downside to what is essentialy adding a large overdose of additve to your gas, however. Additives are heavy molecules and as such they tend to end up in your oil. If you use this method, you will add a greater than normal amount of additive to your oil and that will affect its properties. The way around this is to use the valve cleaner additive and then change your oil after you're done with that tank of gas. In other words do this only when you're near an oil change. There is another possibility, and that's that the valve cleaner additive you use is the same as what's in the gas you use. In which case it will do little good.

Overall, I'd just buy gas from a major brand, and then switch at 5000 miles (or use the 5000 and 1000 mile method). If you have to store your Vette (thank God I live in Texas), leave as little gas in it as possible.

Tom
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#3 (permalink) Old 03-25-2005, 02:34 PM
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wow,,,nice reading,,,good topic good job

visit me at <a href='http://www.storme.co.uk' target='_blank'>www.storme.co.uk</a>

visit me at http://www.janspeed.com
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#4 (permalink) Old 03-25-2005, 10:27 PM
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no, bad job. especially this utter crap about switching gas to get different additives to clean deposits out. where is the solubility argument?? there is absolutely no guarantee techron dissolves shell's tar...

IMMUNE SYSTEM?? antibiotics??! are you on crack?

peter (credentials wise: m.d., and phd in immunology, currently faculty at johns hopkins)

and since late '80 aromatics are out the door due to evap in most states, like cali... please account for this, despite your impressive credentials this post irks me somehow.... NOT A FLAME, just exuberant
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#5 (permalink) Old 03-26-2005, 06:38 AM
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This is an interesting article. I also thought about how one additive would effect the other? used

Now this guy has a good resume and he may have just wrote broad strokes, figuring people would take his word for it. Not sure?

I have been driving a '96 Jeep since new and it has 165K miles on it. I run pretty much the same gas on a regular basis and it runs as it did when I first bought it, so I am not sure I buy the article fully, but it is just one car.

Enjoy,
Curt
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#6 (permalink) Old 03-26-2005, 08:09 AM
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One thing I did learn from this is that I'm an idiot!! used

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#7 (permalink) Old 03-26-2005, 10:34 AM
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The guys a chemist, not a linguist or creative writer, the "immune" "analogy" might not be accurate, but would I rather trust a chemist with his pedigree in the oil field to judge gasoline, or a doctor with an MD degree specializing in immunology. This isn't meant to flame you, but to say at some point you have to trust some one. I chose to trust some one who has the experience to back it up. There is a lot of anecdotal experience out there which just isn't that accurate; this is something you should be able to relate to in the medical field. How many whacked out theories have you heard related to medicine from well intention, but misinformed people.

For example, in the auto industry for years many have been saying that most of the over the counter fuel and oil additives are a waste of money, and you'll read about how great some of them are here in these forums. Heck, I've had my mechanic at Chevron, a man in the business for thirty years tell me not to waste my money on the over the counter stuff he sells. Or how about the phony horse power claims on some of the items sold to a horse power hungry audience - most of it crap. That's why on some of the automotive TV programs, the only horse power claims are those seen on the graph, not word of mouth claims.


The guy is giving an "insider" trick on how to clean engines. So what is the medical field "insider" trick to clean engines?
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#8 (permalink) Old 03-26-2005, 05:18 PM
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Quote:
Originally posted by rsn48@Mar 26 2005, 10:34 AM
The guys a chemist, not a linguist or creative writer, the "immune" "analogy" might not be accurate, but would I rather trust a chemist with his pedigree in the oil field to judge gasoline, or a doctor with an MD degree specializing in immunology. This isn't meant to flame you, but to say at some point you have to trust some one. I chose to trust some one who has the experience to back it up. There is a lot of anecdotal experience out there which just isn't that accurate; this is something you should be able to relate to in the medical field. How many whacked out theories have you heard related to medicine from well intention, but misinformed people.

For example, in the auto industry for years many have been saying that most of the over the counter fuel and oil additives are a waste of money, and you'll read about how great some of them are here in these forums. Heck, I've had my mechanic at Chevron, a man in the business for thirty years tell me not to waste my money on the over the counter stuff he sells. Or how about the phony horse power claims on some of the items sold to a horse power hungry audience - most of it crap. That's why on some of the automotive TV programs, the only horse power claims are those seen on the graph, not word of mouth claims.


The guy is giving an "insider" trick on how to clean engines. So what is the medical field "insider" trick to clean engines?
[snapback]318679[/snapback]
Your absolutly right. Alot of manufacturers now recomend using additives every once and a while....
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#9 (permalink) Old 03-27-2005, 12:44 AM
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yep, the only good additive to add to any sort or lugiud containing in your car is fuel injector cleaner in your gas. It works. Period. stupid "as-seen-on-tv" OIL additives will do just that, add. it'll add another sort of material because its not chemicaly the same as engine oil. for instance, oil addittives that contain "Teflon". Yea that stuff is sure slippery, but it doesnt belong in an engine crankcase. You see Teflon is naturally a solid. So in due time, with the heat from the engine, all those teflon molecules will build up and just add to that "gunk" that the product was supposedly cure. Which makes sense for switching brands of gas, as stated by forum member rsn48, because gas companies do add their own "blend" of additives themselves and gasoline is sort of a solvent type of liguid so theoretically it will clean a fuel system to an extent though.

now for the octane part, its very simple. engine knock is basically detonation. detonation is bad. Detonation is when the air/fuel mixture in the compression stroke of an engine is prematurely ignited. octane helps by: raising the temperature of the fuels igniting point, and making it burn more evenly and cleanly (not cleanly as in less emissions, but more of how efficient the fuel combusted).
usually, and i bet this goes foralmost all the members here, its good to fork out that extra cash for the good ol supreme juice. I mean, Cmon, we all have a "heavy" gas foot on us here. So in general when you want your baby to perform when you need her too, make sure she gets same from you.
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#10 (permalink) Old 03-27-2005, 02:39 PM
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Good read, but I'm a little disappointed since a majoriy of us here drive BMWs and not 1967 Corvettes with carbuerator systems.

I was also hoping one of the articles would awnser the intial question posed concerning the mystery of the Gasoline grades.

Why is or isn't 91 + octane better than 89 and lower?

I have used 89 , 91 , 92, 93 and Ultra 94 octane in my 4 cylinder 1995 E36 318i from whn I bought my car a year ago to now and I notice a tremendous performance leap between the octanes as I increased the number. I'm not sure why it was so, or was it real? also am I getting better gas milage with higher octane or lower?

Now I normally use the highest octane I could find and thats is usually 93.

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#11 (permalink) Old 03-27-2005, 05:50 PM
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Hi Guys !

Your car's octane requirements are mainly determined by its basic design. In addition, variations in engines due to manufacturing tolerances can cause cars of the same model to require a different octane of several numbers. Also, as a new car is driven, its octane requirement can increase because of the buildup of combustion chamber deposits. This continues until a stable level is reached, typically after about 15,000 miles. The stabilized octane requirement may be 3-6 numbers higher than when the car was new. Premium or midgrade fuel may be advisable to prevent knock.

Other factors also influence your car's knocking characteristics:
Temperature - Generally, the hotter the ambient air and engine coolant, the greater the octane requirement.

Altitude - The higher the altitude above sea level, the lower the octane requirement. Modern computer-controlled engines adjust spark timing and air-fuel ratio to compensate for changes in barometric pressure, and thus the effect of altitude on octane requirement is smaller in these vehicles.

Humidity - The drier the air, the greater the octane requirement. The recommendations that vehicle manufacturers give are for normal- to low-humidity levels.

Your engine's spark timing - The octane requirement increases as the spark timing is advanced. Both the basic setting of the spark timing and the operation of the automatic spark advance mechanisms are important in controlling knock. In some computer controlled engines, the spark timing can only be changed by replacing modules in the computer. If they are equipped with knock sensors, these computer controlled engines have the ability to retard the ignition temporarily when a sensor detects knock. This temporarily reduces the octane requirement and may also temporarily reduce vehicle performance.

Method of driving - Rapid acceleration and heavy loading, such as pulling a trailer or climbing a hill, may result in a greater octane requirement. Stop-and-go driving and excessive idling can increase octane requirements by causing the buildup of combustion chamber deposits.

Malfunctions of emission control systems - An improperly functioning emissions control system can affect the octane requirement by changing the air-fuel mixture or by not providing dilution gases through the exhaust gas recirculation (EGR) system. If a malfunction occurs, your vehicle should be taken to a qualified vehicle service mechanic. Some problems are indicated by warning lights on the driver's instrument panel.
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#12 (permalink) Old 03-27-2005, 05:59 PM
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let the chemist bite on this:

1. you absolutely must use the minimum specified octane.
2. typically, there is no advantage in using higher octane.

1. modern cars compensate for low octane, mainly by retarding ignition. this is becasue low octane detonates (high flame advance in combustion chamber). knock sensors "hear" this (they are acoustic sensors), and send signal to the computer, which retards ignition according to the pre-determined map. however, there are limits to which this can occur, and if the octane is too low, the car will detonate no matter what. and be slow. and possibly overheat and crack the head.

2. high octane will detonate less. so the computer can advance ignition, and make your car go faster. usually this is again limited by the pre-set map, and by the camshaft overlap and cam profile. so in cars not designed for this (read all street bmw), there is little advantage to high octane. please note that your car is already operating on the highest rating available in the street in the us.

there are other issues here, such as evap temps, and "energy density", but not directly relevant to your question. we can talk though if you'd like.

also, deposits are bad cos they can act as an ignition point, and cause detonation this way. so having good additives is actually important, not only from the flow perspective (bmw deposit test relies on valve weights, not really combustion chamber depostis, last time i read about it).


clear, somewhat?

peter

ps sorry but this immunology analogy pissed me off too much, i am sensitive about this stuff ghead
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#13 (permalink) Old 03-27-2005, 06:01 PM
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zibby you my man, we almost posted at the same time, sorry for repetitions,

peter
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